There exist methods for converting lignocellulosic biomass into fermentable C5 sugars. Several of these methods first produce oligomers of the C5 sugars, which are then hydrolyzed to form fermentable streams of monomers of C5 sugars. Problems exist with current methods, including, inter alia, that the soluble higher molecular weight oligomers recondense back to insoluble oligomers. To counter this problem, the methods may be performed to drive the hydrolysis of the biomass towards monomer. However, these more stringent conditions often lead to degradation products, such as acids that inhibit fermentation. Also, there are separation challenges as well. It would, therefore, be beneficial to develop methods that avoid this tradeoff to maximize monomer formation and to minimize the formation of degradation products. The methods and compositions of the present invention are directed toward these, as well as other, important ends.